Tertiary alkylaryloxy alkylols



Patented Mar. 30, 1937 v UNITED STATES 2,075,018 "T ERTIARY ALKYLARYLOXYALKYLOLS Herman A. Bruson, Elkins Park, and Otto Stein, Lansdowne, Pa.,assignors to Biihm & Haas Company, Philadelphia, Pa.

No Drawing. Application November 30, 1934, Serial No. 755,358

11 Claims.

This invention relates to new ether alcohols having the general formulaAR,---R wherein R represents an aromatic ring, A represents a tertiaryalkyl group containing at least eight 5 carbon atoms as a nuclearsubstituent' of R; and

R represents a monohydroxy or dihydroxy-alkylene radical, which maycontain one or more sulfo groups.

These new ethers in the unsulfated form are high boiling, colorless oilswhich, in contrast to the known lower homologous phenoxyalkylols, areodorless, insoluble in water, and readily soluble in aliphatichydrocarbons such as lubricating oils. On account of their oily andpenetrant qualities, their unctuous nature, and their freedom from odoror rancidity, these new ethers are useful as textile lubricants, or aslubricants for fine mechanisms such as watches. They are furthermoreuseful in the manufacture of wetting, emulsifying or detergent materialsas for example, by the sulfonation or sulfation respectively of group Ror R They may also be employed as plasticizers for synthetic resins, andfor coating compositions comprising oleoresinousvarnishes, celluloseesters or cellulose ethers. When used in the form of their sul'fonatedderivatives or in the unsulfonated condition they maybe added toinsecticides, cosmetics, soaps, tanning materials, or dyestuifs in order.to obtain better dispersions thereof, or for improving theirproperties.

The raw materials required for the preparation of these new etheralcohols are tertiary alkylphenols containing at least eight carbonatoms in the tertiary alkyl group, as obtained by condensation oftertiary olefines; for example, diisobutylene, dibutenes,.triisobutylene, tetraisobutylene, diisoamylene and the like, withphenols, cresols, xylenols, naphthols, guaiacol, and similar phenols ortheir nuclear halogenated derivatives, as described in copending patentapplications, Serial Nos. 600,826, filed March 23, 1932, by W. F. Hester(now Patent No. 2,008,017), 697,928, filed November 14, 1933 by H. A.Bruson (now Patent No. 1,987,228), and also as described in Journal ofAmerican Chemical Society, 55, 2571 (1933).

These tertiary alkylphenols condense readily in the presence of smallquantities of alkali metal hydroxides or carbonates, with alkyleneoxides such as ethylene oxide, propylene oxide, or isobutylene oxide toyield the corresponding alkylphenoxyalkylols. In place of the alkyleneoxides, the alkvlene halohydrines such as ethylene chlorhydrine,propylene chlorhydrine, glycerol chlorhydrine, isobutylene chlorhydrine,and the like, can be used, in which case the phenols are used preferablyin the form of their alkali metal phenates. In both cases it ispreferable to conduct the condensation in an anhydrous inert solventsuch as alcohol, toluol, butanol, or acetone, at moderate temperatures(50-125 C.) The presence of the tertiary alkyl group having eight ormore carbon atoms in the aromatic ring ortho, meta or para to the ethergroup contributes to these new ether alcohols the property of lowviscosity, high penetration, and unusual stability towards oxidation.

Example 1 a, a, -tetramethylbutylphenoxyethanol (a) A mixture of 50grams of a, a, 'y, -tetramethylbutylphenol (m. p. 84 C.) 1 gram powderedsodium hydroxide and 100 grams dryethyl alcohol was refluxed for 15minutes so as to dissolve the alkali. To the cooled solution thusobtained. a solution of 40 grams ethylene oxide in 100 grams ethylalcohol was added and the mixture allowed to stand 18-24 hours at iii-15C. under an emcient reflux condenser. The mixture was then heated on awater bath for 3 hours at 50-55" C. and finally for 3 hours at -82 C.The alcohol was then distilled off and the residual oil fractionatedunder reduced pressure. The product distilled at 152-164. C. at 1-2 m.m. as a colorless odorless oil, insoluble in water, but readily sol ublein most organic solvents. The yield was 91% of theory. (b) A mixture of103 grams of a, a, 'y, 'y-tetramethylbutylphenol, 75 grams nbutanol, 75grams toluene and 22 grams sodium hydroxide was boiled under reflux. Thewater which formed was continuously removed while the butanol-toluenemixture was automatically restored to the reaction vessel. After 2-3hours of boiling, 9 grams of water were collected, showing that theformation of the dry sodium ter-octylphenate was complete. To the clearpale brown solution obtained, 44 grams powdered sodium hydroxide wasadded, the mixture cooled to about 5 C. and 120 grams ethylenechlorhydrine added all at once. The mixture was stirred vigorously for5-6 hours at 5-15" C. gradually increasing the temperature to 20-25 C.and allowing the mixture to react thereat for 6-8 hours. Finally themixture was warmed to about C. during 12 hours. The sodium chloridewhich separated was filtered off and the filtrate distilled,

n.. t at ordinary pressure to recover the solvents and finally in vacuo.The product came over at 170-175" C./3-4 mm. in a yield amounting to 113grams.

5 Sulfation of the above ether (b) 40 grams of the above ether alcoholwas dissolved in 280 grams ethylene dichloride. The solution was cooledto 0-5" C. and 30 grams of 100% sulfuric acid added dropwise theretoduring minutes while maintaining the temperature below 10 C. The mixturewas then stirred for 2 hours at this temperature, then placed in aseparatory funnel and allowed to reach room 15 temperature. Two layersformed, the lower of which was sulfuric acid which was run off. The

It was soluble in water to give a foamy solution of extremely lowsurface tension, and having powerful wetting-out properties. Thepotassium and ammonium salts are similar in their properties to theabove sodium salt.

Example 2 The phenol used was ter-iso-duodecylphenol, a condensationproduct of tri-isobutylene and phenol having the empirical formula Thismaterial was prepared by condensing comniercial trisobutylene withphenol in the presence of concentrated sulfuric acid. It formed a 5viscous, partly waxy oil possessing a boiling range of 132-l45 C./3-4mm. A mixture of one mol. of this triisobutylenephenol, 2 grams powderedcaustic soda and 1.8 mols ethylene oxide was condensed in alcoholsolution as described in Example l. Thetertiary-iso-duo-decylphenoxyethanol.

O-CHrOHzOH Cn uformed a. colorless oil, boiling range Mil-185 C./4 mm.Upon sulfation with concentrated surfuric acid as described in Example1, it gave a watersoluble sulfuric acid ester which when neutralizedwith caustic soda in the cold, gave a foamy, soapy solution from whichon evaporation, a brittle resin was obtained having good wetting-outproperties.

Example 3 The phenol used was ter-isohexadecylphenol, the condensationproduct of tetra-isobutylene (boiling range 224-259 C.) and phenolprepared by means of concentrated sulfuric acid as a cotalyst. It formeda colorless waxy mass boiling at l30-165 C./2 mm. 1 mol. equivalent ofthis material was condensed with ethylene chlorhydrine and caustic sodaas described in Example 1. The product,tertiary-isohexadecylphenoxyethanol C "Hilformed a colorless oil,boiling range 140- 10 172 C./3 mm. Upon sulfation it gave a soap-likeproduct having good wetting-out properties.

Example 4 The phenol used was ter-isooctylphenol of boil- 15 ing range137-142 C./2 mm. as prepared by the condensation of phenol and thedibutene fraction of b. p. 106-116 C. (obtained by the copolymerizationof the three isomeric butenes by means of concentrated sulfuric acid).20

The above ter-iso-octyl phenol was condensed with ethylene .oxide in thepresence of potassium hydroxide as described in Example 1. The product,ter-isooctylphenoxyethanol, was a colorless oil b. p. 145-150" C./2 mm.25

Example 5 A mixture of 103 grams a, on 'y, -y-tetramethylbutylphenol, 22grams sodium hydroxide, 250 ccm. alcohol and 115 grams glycerolmonochlor- 30 hydrine was stirred for 24 hours at 20-30 C., then heated6 hours at 70-80 C. The sodium chloride was filtered oil, the filtratewashed with water and the oil layer distilled to recover the solvents.

The residual oil has the probable formula:

on. (i111 O-CHz-CH-ClIaOH CH;-CH (J H 40 It formed a colorless viscousoil boiling at 215- 220 C./7 mm. When esterified with 1 mol. or 2 mol.equivalents concentrated sulfuric acid at 0-5 C. and the productneutralized with ammonia, an excellent wetting agent is obtained. 45

Example 6 To a stirred mixture of 96 grams a, a, 'y,'ytetramethylbutyl-monochlorphenol (b. p. 128- 134" C./2 mm.) 200 gramsalcohol, and 27 grams 50 sodium hydroxide, there was added dropwise, asolution of 48 grams ethylene chlorhydrine in 50 grams alcohol during 3hours. The mixture was allowed to stand 18 hours at 25 C. and thenheated with stirring on a water bath up to 70 C. dur- 55 ing 6 hours.The sodium chloride was then filtered off and the filtrate fractionated.The product, a, a, 'y, -tetramethylbutyl-chlorphenoxyethanol came overat 194 C./6 mm. as a viscous pale oil. 0

Example 7 To a solution of 50 grams a, a, 'y, 'y-tetramethylbutylphenolin grams alcohol containing 1 gram sodium hydroxide there was added withcooling to 0 C. a solution of 16 gr. propylene oxide in 50 gramsalcohol. The mixture was allowed to stand 24 hours at 20 C., then heatedUsing 23 grams isobutylene oxide in place of 7 the propylene oxide asshown in Example 7, there was obtained 59 grams of a, a, 'y,-tetramethylbutylphenoxy tertiary butanol boiling a 145 C./1-2 mm.

5 As in the above examples, the tertiary alkyl group is advantageouslyderived from an oleflne polymer of isobutylene, i. e., a dipolymer,tri-polymer, or tetrapolymer; since these bodies are the most readilyaccessible tertiary oleflnes containing respectively 8, 12, and 16carbon atoms which are capable of forming the corresponding long chaintertiary alkyl phenols on condensation with phenols However. thepolymers of isoamyiene, hexylene, heptene, octene and the like, havingtertiary unsaturated carbon atoms are likewise suitable for the purposesherein.

It is understood that the above examples are given merely by way ofillustration and not limitation. It is apparent to one versed in the art20 that wide deviations are possible in starting materials,temperatures, conditions of operation, pressure, etc., without departingfrom the spirit of the invention, the scope of which is limited only bythe following claims. The sulfates of the alcohols herein claimed arethe subject matter of a divisional application Serial No. 97,347 filedfiled August 22, 1936.

We claim:

1. The process of preparing new ether alcohols 80 which comprisesreacting upon a phenol having a nuclear tertiary alkyl group of at leasteight carbon atoms, in the presence of, an alkali, with a member of thegroup consisting of alkylene oxides and alkylene chlorhydrines.

2. A process of preparing new ether alcohols which comprises reactingupon a phenol having a nuclear tertiary alkyl group of at least eightcarbon atoms, in the presence of an alkali metal hydroxide, with amember of the group consisting of alkylene oxides and alkylenechlorhydrines.

3. A process of preparing new ether alcohols which comprises condensingethylene chlorhydrine with an alkali metal salt of a tertiary alkylphenol having at least eight carbon atoms in the tertiary alkyl group. a

4, A process of preparing new ether alcohols which comprises condensingethylene oxide in the presence of an alkali metal hydroxide with atertiary alkylphenol having at least 8 carbon atoms in the tertiaryalkyl group.

5. A process which comprises heating an alkali metal salt of alpha,alpha, gamma, gamma-tetramethylbutyl phenol with ethylene chlcrhydrine.

6. A process which comprises heating ethylene oxide with alpha, alpha,gamma, gamma-tetramethylbutylphenol in the presence of a small quantityof caustic alkali.

7. An ether alcohol-of'the formula o-omomon said compound being an oilboiling at about 152-164 C./2 mm.

9. A compound of the formula wherein A represents a tertiary alkyl groupcontaining from 8 to 16 carbon atoms inclusive, and R represents amember of the group consisting of monohydroxy alkyl anddihydronalkylradicals.

10. A compound of the formula said compound being an oil boiling atabout 215-220 C./'7

11. As a new compound a, a. '1. 'Y-tetramethyl phenoxy propanol.

' HERMAN A. BRUSON.

O'II'O STEIN.

